FOUNDATION IN MEDICAL STUDIES (JULY 2013 INTAKE) CHM1024 LABORATORY REPORT PRACTICAL 5 : REACTIONS OF ALDEHYDES AND KETONES

NAME MATRIX ID GROUP SEMESTER DATE LECTURER

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AKMAL ADIB BIN FADZIL CPM0018_2013C A TWO 21st JANUARY 2014 MR. MOHD YUSOFF HUSSAIN

OBJECTIVE The objective of this experiment is to differentiate between aldehydes and ketones using qualitative analysis.

INTRODUCTION In organic chemistry, a carbonyl group is a functional group composed of a carbon atom double bonded to an oxygen atom, C=O. Aldehydes and ketones are belonged to this group. While both molecules have a carbonyl group, they differ in what atom is bonded to the carbonyl carbon. The carbonyl carbon of an aldehyde is bonded to a hydrogen atom and one carbon atom. The carbonyl carbon of a ketone is bonded to two carbon atoms. Aldehydes and ketones are commonly found in sugars, flavours, steroids and intermediates in biological chemical production. Aldehyde Ketone

One of the properties of aldehydes and ketones is intermolecular forces. The only intermolecular forces are Dipolar and LDF. The double connection makes the CO double bond even larger dipole than a CO single bond and therefore exerts a more attractive force than ethers. Another one of the physical properties of aldehydes and ketones is solubility. Aldehydes and ketones cannot give a H-bond but they can receive two H-bonds from water since the carbonyl has two lone pairs. Since they have a larger dipole than alcohols, water will form a stronger H-bond to them. This balances out to ake the aldehydes and ketones to have about the same solubility in water as a similar sized alcohol. Besides that, since they cannot give a H-bond the only forces that hold the molecules of the pure substance together is dipole-dipole attractions and LDF attractions. A carbonyl is more polar than an ether connection so we expect the melting and boiling point for similar sized aldehydes and ketones to be higher than ethers and lower than alcohols. Aldehydes and ketones are neutral (neither acidic nor alkaline). One of their chemical properties is that all aldehydes and ketones are flammable. The lower molecular weight ones which have a lower boiling point will be more volatile (evaporate more) and therefore have the potential for flashing or explosion (rapid oxidation) due being 2

premixed with oxygen in the air. Liquids and solids only burn at the surface and are limited by the amount of oxygen that gets to them. Gases mixed with oxygen can burn all at once. Besides that, aldehydes can be oxidized to carboxylic acids. Ketones are not easily oxidized. This is one way to distinguish between the aldehydes and the ketones. Furthermore, aldehydes and ketones can undergo addition reactions. An addition reaction is where a whole molecule is added across the double bond and it becomes a single bond. In addition, both aldehydes and ketones can be reduced. This type of addition reaction is where H2 is added to the carbonyl to give the corresponding alcohol. Aldehydes can be reduced, [H], back to primary alcohols and ketones can be reduced to secondary alcohols by the addition of H2 and a catalyst. Aldehydes and ketones can both react with alcohols (usually under acid conditions) to form an addition product. Any alcohol should react but usually the alcohols chosen are small like methanol or ethanol. Aldehydes add to the first alcohol to become a hemi-acetal and then add to a second alcohol to form a stable acetal and release water. Ketones add the first alcohol to become a hemi-ketal and then add a second alcohol to form a stable ketal and release water.

For this experiment, several tests will be conducted to identify two unknown solutions where at the end of this experiment, one of the solutions will be identified as aldehyde while the other one is ketone. The test are Bradys Test, Fehlings Test, Tollens Test and Schiffs Test.

APPARATUS AND MATERIALS 1. Unknown A. 2. Unknown B. 3. 2, 4 dinitrophenylhydrazine (Bradys reagent). 4. Fehlings solution. 5. 250 ml beaker. 6. Bunsen burner. 7. Wire gauze. 8. Tripod stand. 9. 2.5 M sodium hydroxide, NaOH solution. 10. 0.3 M silver nitrate, AgNO3 solution. 11. 5 % ammonia, NH3 solution. 12. Droppers. 13. Schiffs reagent. 14. Distilled water. 15. Rubber stopper. 16. 10 test tubes. 17. Water bath maintained at 70. 18. Labelling stickers.

METHOD A. Bradys Test. (2, 4 DNPH) 1. 1 ml of Unknown A and Unknown B are placed into two separate test tubes and labelled. 2. A few drops of 2, 4 dinitrophenylhydrazine (2, 4 DNPH) are added into each test tube. 3. The test tubes are shaken and heated in the water bath for 5 10 miutes. The formation of precipitate is observed. 4. 2 ml of distilled water is added if no precipitate forms. 5. All observations are recorded. B. Fehlings Test. 1. 1 ml of Unknown A and Unknown B are placed into two separate test tubes and labelled. 2. 2 ml of Fehlings solution is added into each test tube. 3. The test tubes are shaken gently. 4. The mixture is heated in boiling water for 15 20 minutes. Any formation of precipitate is observed. C. Tollens Test. 1. Tollens reagent is prepared by adding one drop of 2.5 M NaOH solution into 2 ml solution of 0.3 M AgNO3 in a test tube. 2. 5 % NH3 solution is added drop by drop until the precipitate dissolves. 3. 1 ml of Unknown A and Unknown B are placed into two separate test tubes and labelled. 4. 1 ml of Tollens reagent is added into each test tube and the mixtures are shaken gently. 5. The mixtures are allowed to stand for 3 minutes. Both test tubes are then observed to see whether a silver mirror is formed in any of the test tubes. 6. The mixture is warmed in the water bath at 70 for 5 minutes if the silver mirror does not form. 7. All observations are recorded.

D. Schiffs Test. 1. 1 ml of Unknown A and Unknown B are placed into two separate test tubes and labelled. 2. 1 to 3 drops of Schiffs reagent is added into each test tube. 3. The test tubes are shaken gently. Any changes in colour are noted. 4. If any of the compounds does not dissolve, the test tube is closed with a rubber stopper and shaken vigorously until an emulsion is formed. Any observations are recorded.

RESULTS OBSERVATION TEST UNKNOWN A The colour changes from colourless to yellowish orange Bradys Test precipitate. The precipitate remains unchanged when heated in water bath and added with distilled water. The blue colour of the mixture remains unchanged. UNKNOWN B The colour changes from colourless to yellowish orange precipitate. The precipitate emulsifies when heated in water bath. The colour of the mixture has changed from blue into red. A brickred precipitate is formed. Silver precipitate is formed and eventually a silver mirror is formed. The colour of the solution turns from light pink to dark purple. An emulsion is formed.

Fehlings Test

Tollens Test

The mixture remains unchanged.

Schiffs Test

The colour of the solution turns from light pink to magenta.

DISCUSSIONS Bradys Test. For the first test, a few drops of 2, 4 - DNPH placed in two separate test tubes containing Unknown A and B respectively. The test tubes are shaken to allow the mixture to dissolve. This step is done to qualitatively detect the carbonyl functionality of the ketone or aldehyde functional group. A positive test is signalled by a yellow, orange or red precipitate known as 2, 4 - dinitrophenylhydrazone. If the carbonyl compound is aromatic, then the precipitate will be red; if aliphatic, then the precipitate will have a more yellow colour. In this test, both of the unknowns turn yellowish orange in colour when added with 2, 4 DNPH which means both solutions are aliphatic compounds.

Mechanism of reaction of an aldehyde with 2, 4 DNPH to form 2, 4 dinitrophenylhydrazone.

Mechanism of reaction of a ketone with 2, 4 DNPH to form 2, 4 dinitrophenylhydrazone.

Both of the reactions above can be described as a condensation reaction as two molecules joining together with loss of water. It is also considered an addition-elimination reaction because the first reaction is a nucleophilic addition of the -NH2 group to the C=O carbonyl group and followed by the removal of a H2O molecule.

The test to identify the unknowns continues by using derivatization technique. Both test tubes (containing 2, 4 dinitrophenylhydrazone) are heated in a water bath for 5 10 minutes. Mixture containing Unknown B emulsifies while the other one remains unchanged even when added with distilled water. In the end, it can be said that the Unknown B is an aldehyde while Unknown A is ketone.

Fehlings Test. For this test, 2 ml of Fehlings solution is added to two separate test tubes containing Unknown A and B respectively. Both mixtures in the test tubes are then shaken and heated in boiling water for 15 20 minutes. After the heating process, it is observed that the blue colour of the mixture containing Unknown B has changed from blue into red and a brick red precipitate is formed while the mixture containing Unknown A remains unchanged. Therefore it can be said that Unknown B is an aldehyde while Unknown A is a ketone. The reason for the above statement is that Fehlings solution contains bistartratocuprate (II) complex which is an oxidising agent (which is also the active reagent in the test) and therefore it needs a reducing agent for a redox reaction to occur. Aldehydes are a reducing agent so it will react with the bistartratocuprate (II) complex in the Fehlings solution to form a redox reaction. The bistartratocuprate(II) complex oxidizes the aldehyde to

a carboxylate anion, and in the process the copper(II) ions of the complex are reduced to copper(I) ions. Red copper(I) oxide then precipitates out of the reaction mixture which forms into the brick red precipitate that has been observed above. The carboxylic acid produced reacts further with the alkali to for a salt, carboxylate (RCOO-) and water.
Mechanism of reaction of aldehyde and Fehlings solution.

Ketones do not react with Fehlings solution because ketones are not a reducing agent. Therefore, they do not react with the bistartratocuprate (II) complex in the Fehlings solution to form a brick red precipitate.

Tollens Test. Before starting this experiment, Tollens reagent is needed to be prepared by mixing one drop of 2.5 M NaOH solution into 2 ml solution of 0.3 M AgNO 3 in a test tube and adding 5% NH3 solution is added drop by drop until the precipitate dissolves. This is because Tollens reagent is not commercially available due to its short life. Because of that, this reagent is prepared freshly in the lab and used for the experiment immediately. To start this experiment, 1 ml of Unknown A and Unknown B is added into two separate test tubes and followed by adding 1 ml of Tollens reagent into each test tube. Both test tubes containing the mixture are shaken gently and allowed to stand for 3 minutes. After 3 minutes, it is observed that both of the mixtures remained unchanged. Therefore, both test tubes are warmed in a water bath for 5 minutes. At the end, it is observed that silver precipitate formed in the test tube containing Unknown B and eventually silver mirror is formed in the test tube. The other test tube which contains Unknown A remains unchanged. Therefore, it can be deducted that Unknown B is an aldehyde while Unknown A is a ketone. This is because aldehydes are more readily oxidised compared to ketones which is due to the carbonyl-containing carbon in aldehydes having an attached hydrogen. The diamminesilver (I) complex in the mixture is an oxidizing agent and is the essential reactant in Tollens' reagent. When Tollens reagent reacts with an aldehyde, the diamminesilver (I) complex oxidizes the aldehyde to a carboxylate ion and in the process is reduced to elemental silver and aqueous ammonia. The elemental silver precipitates out of solution, occasionally onto the inner surface of the reaction vessel, giving a characteristic "silver mirror". The carboxylate ion on acidification will give its corresponding carboxylic acid. The carboxylic acid is not directly formed in the first place as the reaction takes place under alkaline conditions. The general equation for the overall reaction is shown below: RCHO + 2[Ag(NH3)2]+ + OH- RCOO- + 2Ag(s) + 2NH4+ +2NH3 The ionic equations for the reactions are as follows: [Ag(NH3)2]+ (aq) + e Ag (s) + 2 NH3 (aq) RCHO (aq) + 3 OH RCOO + 2 H2O + 2 e Ketones do not produce a silver mirror or silver precipitate when it reacts with Tollens reagent because ketones cannot be oxidized easily. Ketones have no available hydrogen atom attached to the carbonyl carbon, meaning it cannot be so easily oxidized unlike an aldehyde which has this hydrogen atom.

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Schiffs Test. The Schiff test is an early organic chemistry name reaction developed by Hugo Schiff and is relatively general chemical test for detection of many organic aldehydes that has also found use in the staining of biological tissues. The Schiff reagent is the reaction product of a dye formulation such as fuchsin and sodium bisulfite; pararosaniline (which lacks

an aromatic methyl group) andnew fuchsin (which is uniformly mono-methylated ortho to the dye's amine functionalities) are dye alternatives with comparable detection chemistry. For this experiment, 1 3 drops of Schiffs reagent is added into 2 test tubes which contains Unknown A and B respectively. Both test tubes are shaken gently. For Unknown A, the light purple colour of the Schiffs reagent changes into magenta with no emulsion. For Unknown B, the light purple colour of the Schiffs reagent changes into dark purple with an emulsion. Theoretically, an aldehyde reacts with Schiffs reagent to produce a magenta colour which is a positive result while ketones do not react with Schiff s reagent. Therefore, it can be said that there was an error in this experiment which may be caused by an expired Schiffs reagent or accidentally mixing other substance into the test tube or the test tube is not cleaned properly and thoroughly. Precautions. Throughout the experiment, several precautions are taken and noted. One of them is to wear lab coats and protective gloves to prevent the substances and reagent used in the experiment to spill into the clothes and hands in case the experiment is not properly conducted as some of them are hard for the stain to wear off. Besides that, the wastes of the experiment (used substances and reagents) should be discarded in a special beaker provided by the lab instructor. This is because some of the substances and reagents may for other harmful substances. One example is the Tollens reagent. The reagent should be acidified with dilute acid after the test before it is discarded to prevent the formation of the highly explosive silver nitride. Another one is to make sure the test tubes which are going to be used in the experiment is cleansed and rinsed with distilled water to prevent other substances to interfere with the experiment and the results obtained.

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CONCLUSION In conclusion, it can be deduced that Unknown A is a ketone while Unknown B is an aldehyde by using qualitative analysis from Bradys Test, Fehlings Test, Tollens Test and Schiffs Test. Unknown B which is an aldehyde is more reactive than Unknown A which is a ketone. This is caused by the functional group of the aldehyde which contains a hydrogen atom and an alkyl group that makes it less stable than ketone which does not have the hydrogen atom but instead 2 alkyl groups.

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QUESTIONS 1. What causes the silver mirror to form in carbonyl compounds in Tollens Test? The formation of silver mirror in Tollens Test is caused by the reduction of silver nitrate ions, [Ag(NH3)2]+ into grey metallic silver compound by aldehyde which is a reducing agent. 2. Explain the iodoform test on carbonyl compounds. The aldehyde or ketone is mixed with aqueous sodium hydroxide. After that, iodinepotassium iodide solution is added to the mixture. The yellow precipitate that is formed give an indication that both aldehyde and ketone reacts with the iodinepotassium iodide solution to produce acetaldehyde and methyl ketone respectively. 3. What other test can be carried out to differentiate aldehydes and ketones? Another test that can be carried out to differentiate aldehydes and ketones is chromic acid test (Bordwells Reagent or Jones Reagent). The chromic acid (CrO3) will change in colour from orange to brown to greenish-blue when it oxidises an aldehyde. As for ketones, the colour of the chromic acid will remain orange as ketones do not oxidise.

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REFERENCES 1. CHEMISTRY FOR MATRICULATION SEMESTER 2 FOURTH EDITION, Tan Yin Toon, Oxford Fajar Sdn. Bhd. 2013. 2. http://www.chemguide.co.uk/organicprops/carbonyls/background.html 3. http://spot.pcc.edu/~mdeming/102/Labs/CH102_Lab_5_Aldehydes_and_Ketones.pdf 4. http://myweb.brooklyn.liu.edu/lawrence/che4x/e4aldket.pdf 5. http://employees.oneonta.edu/knauerbr/chem226/226expts/226_expt09_pro.pdf 6. http://faculty.swosu.edu/william.kelly/pdf/ketone.pdf 7. http://www.chem.umass.edu/~samal/269/aak.pdf 8. http://www.wiu.edu/users/mftkv/Chemistry102/oxidationaldehydes.html 9. http://stainsfile.info/StainsFile/stain/schiff/schiffwhatis.htm 10. http://www.scribd.com/doc/96379782/CHEM-II-5 11. http://en.wikipedia.org/wiki/Carbonyl#Carbonyl_compounds

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